FR2915886A1 - TINCTORIAL COMPOSITION COMPRISING A PARTICULAR AMINOPYRAZOLOPYRIDINE OXIDATION BASE, A COUPLER AND A PARTICULAR SURFACTANT - Google Patents

Abstract

The subject of the invention is a dye composition comprising at least one aminopyrazolopyridine base, a coupler and a particular surfactant chosen from (C 8 -C 30) alkyl carboxylic ether acids and their salts, (C 12 -C 30) alkyl polyglucosides and surfactants. The invention also relates to a dyeing process using this composition, wherein the aforementioned dye composition is applied to the fibers in the presence of an oxidizing agent for a time sufficient to develop the desired coloring. Finally, the subject of the present invention is a device with several compartments. The composition of the present invention makes it possible in particular to obtain a coloring with various shades, powerful, aesthetic, not very selective and resistant to the various attacks that the hair can undergo.

Description

TINCTORIAL COMPOSITION COMPRISING AN OXIDATION BASE

  The subject of the invention is a dyeing composition comprising at least one particular aminopyrazolopyridine base, at least one coupler and at least one particular surfactant. DESCRIPTION OF THE PREFERRED EMBODIMENTS The subject of the invention is also the use of this composition for dyeing keratinous fibers as well as the dyeing process using this composition. It is known to dye keratinous fibers and in particular human hair with dye compositions containing oxidation dye precursors, generally known as oxidation bases, such as ortho or para-phenylenediamines, ortho or para-aminophenols and heterocyclic compounds. These oxidation bases are colorless or weakly colored compounds which, when combined with oxidizing products, can give rise to colored compounds by a process of oxidative condensation. It is also known that the shades obtained with these oxidation bases can be varied by combining them with couplers or color modifiers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds such as than indolic compounds. The variety of molecules involved in oxidation bases and couplers, allows to obtain a rich palette of colors.

  The so-called "permanent" coloration obtained with these oxidation dyes must also meet a certain number of requirements. Thus, it must be harmless from the toxicological point of view, it must make it possible to obtain shades in the desired intensity and to have good resistance to external agents such as light, bad weather, washing, permanent undulations, sweating and friction. The dyes must also make it possible to cover the white hair, and finally be the least selective possible, that is to say, to obtain the lowest possible color differences throughout the same keratin fiber, which is in general differently sensitized (ie damaged) between its point and its root.

  It is already known to use aminopyrazolopyridine oxidation bases for dyeing keratin fibers, particularly in the patent application FR 2 801 308. These bases make it possible to obtain various shades.

  It is however desirable to further improve the power of the color obtained, its selectivity, as well as its resistance to external agents. This object is achieved with the present invention which relates to a dyeing composition comprising, in a dyeing medium suitable for dyeing keratinous fibers, one or more aminopyrazolopyridine oxidation bases of formula (I) below: Z-R Wherein X 1 and Z 2 are independently - a single covalent bond, - a divalent radical selected from - a radical -O (CH 2) p -, where p denotes an integer ranging from 0 to A radical ## STR5 ## where q denotes an integer ranging from 0 to 6 and t denotes 0 or 1. R '6 represents a hydrogen atom, a C1-C6 alkyl radical; C6 optionally substituted with one or more hydroxy groups. Z1 can also represent a divalent radical ùS-, -SO-, -SO2- when R'1 is a methyl radical, R'1 and R'2 independently represent: - a hydrogen - a C1-C10 alkyl radical optionally substituted and optionally interrupted by a heteroatom or a group selected from O, N, Si, S, SO, SO 2, a halogen, a SO 3 H radical, a 5 to 8-membered ring, substituted or unsubstituted, saturated, unsaturated or aromatic, optionally containing one or more heteroatoms or groups selected from N, O, S, SO2i -CO-, the ring may be cationic and / or substituted with a cationic radical, a group -N + R17R18R19, R17i R13 and R19 being linear or branched C 1 -C 5 alkyl optionally substituted with one or more hydroxyl groups. When Z, respectively Z2 represents a covalent bond, then R ', respectively R'2 may also represent a radical: - C, -C6 alkylcarbonyl optionally substituted - -O-00-R, ùCO-OR, NR-CO- R 'or CO-NRR' in which R and R 'independently represent a hydrogen atom or an optionally substituted C1-C6 alkyl radical, • R'3, R'4 and R'5, which are identical or different, represent - a hydrogen atom, - a hydroxyl radical, - a C1-C6 alkoxy radical, - a C1-C6 alkylthio radical, - an amino radical, - a monoalkylamino radical, - a C1-C6 dialkylamino radical in which alkyl radicals can form, with the nitrogen atom to which they are attached, a saturated, unsaturated, aromatic or non-aromatic 5 to 8-membered heterocycle which may contain one or more heteroatoms or groups chosen from N, O, S and SO2i CO, the heterocycle may be cationic, and / or substituted by a cationic radical, - an alkylcarbon radical C1-C6 yl, optionally substituted, a -O-00-R, ùCO-OR, NR-CO-R 'or ùCO-NRR' radical with R and R 'as defined previously, - a halogen, - a radical ùNHSO3H, - an optionally substituted C1-C4 alkyl radical, - a saturated, unsaturated or aromatic carbon ring, optionally substituted. R'3, R'4 and R'5 may form, two by two, a partially saturated or non-saturated ring, X represents an ion or group of ions making it possible to ensure the electronegativity of the derivative of formula (I) ,

  with the proviso that at least one of the groups R ', and R'2 represents a cationic radical. One or more couplers, and one or more surfactants selected from (C 8 -C 30) alkylcarboxylic acids and their salts, (C 12 -C 30) alkyl polyglucosides and mono or polyglycerolated surfactants.

  The invention also relates to a dyeing process using this composition. Another subject of the invention is the use of the composition of the present invention for dyeing keratinous fibers, in particular human keratinous fibers such as the hair.

  The composition of the present invention makes it possible in particular to obtain a dyeing composition of keratinous fibers which are suitable for use in oxidation dyeing and make it possible to obtain a coloration with varied shades, powerful, esthetic, not very selective and resistant well to various attacks that hair can suffer such as shampoos, light, sweat and permanent deformities. It should be noted that in what follows, and unless otherwise indicated, the boundaries of a domain of values are included in this area. In the compounds of formula (I) above, the alkyl expression used for the alkyl radicals as well as for the groups comprising an alkyl part, signifies a carbon chain, linear or branched, containing from 1 to 4 carbon atoms, substituted or unsubstituted by one or more heterocycles, or by one or more phenyl groups or by one or more groups selected from halogen atoms such as chlorine, bromine, iodine and fluorine; hydroxyl, alkoxyl, amino, carbonyl, carboxamido, sulphonyl, -CO2H, -SO3H, -PO3H2i -PO4H2, -NHSO3H, sulphonamide, (C1-C4) alkylamino, trialkyl (C1-C4) ammonium radicals, or also with a (C 1 -C 4) -alkylamino radical in which the two alkyl groups can form, together with the nitrogen atom of said dialkyl (C 1 -C 4) amino group to which they are bonded, a cycle which can be interrupted by one or more nitrogen, oxygen or sulfur atoms.

  Similarly, according to the invention, the alkoxy expression used for the alkoxy radicals as well as for the groups comprising an alkoxy part, signifies a linear or branched O-carbon chain containing from 1 to 4 carbon, substituted or unsubstituted by one or more groups selected from heterocycles; halogen atoms such as chlorine, bromine, iodine and fluorine; hydroxyl, amino, carbonyl, carboxamido, sulphonyl, -CO2H, -SO3H, -PO3H2i -PO4H2, -NHSO3H, sulphonamide, (C1-C4) alkylamino, trialkyl (C1-C4) ammonium radicals, or else by a (C 1 -C 4) dialkylamino radical in which the two alkyl groups can form, together with the nitrogen atom of said dialkyl (C 1 -C 4) amino group to which they are attached, a ring which can be interrupted by one or several atoms of nitrogen, oxygen or sulfur. According to the invention, the term "heterocycle" means an aromatic or non-aromatic ring containing 5, 6, 7 or 8 vertices, and from 1 to 3 heteroatoms chosen from nitrogen, sulfur and oxygen atoms. These heterocycles may be fused to other heterocycles or to a phenyl group. They may be substituted by a halogen atom; a (C1-C4) alkyl radical; a (C1-C4) alkoxy radical; a hydroxyl radical; an amino radical; a (C1-C4) alkylamino radical; di (C1-C4) alkylamino wherein the two alkyl groups together with the nitrogen atom to which they are attached form a ring which can be interrupted by one or more nitrogen, oxygen or sulfur atoms. These heterocycles may, in addition, be quaternized with a (C1-C4) alkyl radical. Among these optionally fused heterocycles, there may be mentioned by way of example the rings: thiadiazole, triazole, isoxazole, oxazole, azaphosphole, thiazole, isothiazole, imidazole, pyrazole, triazine, thiazine, pyrazine, pyridazine, pyrimidine, pyridine, diazepine, oxazepine, benzotriazole, benzoxazole, benzimidazole, benzothiazole, morpholine, piperidine, piperazine, azetidine, pyrrolidine, aziridine, 3- (2-hydroxyethyl) benzothiazol-3-ium, and 1- (2-hydroxyethyl) pyridinium. According to the invention, phenyl is understood to mean a phenyl radical which is unsubstituted or substituted by one or more cyano, carbonyl, carboxamido, sulphonyl, -CO2H, -SO3H, -PO3H2, -PO4H2, hydroxyl, amino or monoalkyl radicals (C1- C4) amino, or dialkyl (C1-C4) amino in which the two alkyl groups can form, together with the nitrogen atom of said dialkyl (C1-C4) amino group to which they are attached, a ring which can be interrupted by a or several atoms of nitrogen, oxygen or sulfur. By ring or cationic heterocycle is meant a ring containing one or more quaternary ammonium groups. By way of example of radicals of the -N + R17R18R19 type, mention may be made of the trimethylammonium, triethylammonium, dimethylethylammonium, diethylmethylammonium, diisopropylmethylammonium, diethylpropylammonium, betahydroxyethyl diethylammonium, di (betahydroxyethyl) methylammonium, tri (betahydroxyethyl) ammonium. As an example of cationic heterocycle, there may be mentioned imidazolium heterocycles, pyridiniums, piperaziniums, pyrrolidiniums, morpholiniums, pyrimidiniums, thiazoliums, benzimidazoliums, benzothiazoliums, oxazoliums, benzotriazoliums, pyrazoliums, triazoliums, benzoxazoliums. The compounds of formula (I) may optionally be salified with strong mineral acids such as, for example, HCl, HBr, HI, H 2 SO 4, H 3 PO 4, or organic acids such as, for example, acetic, lactic, tartaric or citric acid. or succinic, benzenesulfonic, para-toluenesulfonic, formic, methanesulfonic. If they have anionic groups such as the groups -CO2H, -SO3H, -PO3H2, -PO4H2, the compounds of formulas (I) may be salified with hydroxides of alkali or alkaline earth metals, such as sodium hydroxide or potassium hydroxide, by ammonia, by organic amines. They may also be in the form of solvates, for example a hydrate or a linear or branched alcohol solvate such as ethanol or isopropanol. In the context of the invention, the term "derivative of formula (I)" means any mesomeric or isomeric forms. By way of examples of derivatives of formula (I), mention may be made of the following compounds in which X- is as defined previously: NH 2 N / NON X ~ N- [2- (3-Amino-pyrazolo [1] salt 5- (3-Amino-pyrazolo [1,5-a] pyridin-2-yl) -1-methyl-3H-imidazol-3- (3-amino-pyrazolo [3-a] pyridin-2-yl) -1-methyl-3H-imidazole salt NH 2 N 1N + X [2- (3-Amino-pyrazolo [1,5-a] pyridin-2-ylamino) -ethyl] -ethyl-dimethyl-ammonium salt NH 2 N / NO X NH 2 2- (3-Amino-pyrazolo [1,5-a] pyridin-2-ylamino) -ethyl] - (2-hydroxy-ethyl) -dimethyl-ammonium N / NO X + - N ~ OH NH 2 Salt of [3] - (3-Amino-pyrazolo [1,5-a] pyridin-2-ylamino) -propyl] -trimethylammonium NO x N + x NH 2 NO X, N [4- (3-Amino-pyrazolo) salt [1,5-a] pyridin-2-ylamino) butyl] trimethylammonium NH 2 NH 4 -NHCl [5- (3-Amino-pyrazolo [1,5-a] pyridin-2-ylamino salt) -pentyl] -trimethylammonium NH 2 NH / NON-N-methyl-3- [2- (3-Amino-pyrazolo [1,5-a] pyridin-2 -ylamino) -ethyl] -1-methyl-3H-imidazol-1-ium NH 2 N ~ + / X 3- [3- (3-Amino-pyrazolo [1,5-a] salt pyridin-2-ylamino) -propyl] -1-methyl-3H-imidazol-1-ium 3- [3- (3-Amino-pyrazolo [1,5-a] pyridin-2-ylamino) -propyl salt 1- (2-Hydroxyethyl) -3H-imidazol-1-NH 2 -NH-N-O -ium salt of 3- [2- (3-Amino-pyrazolo [1,5-a] pyridin-2-yloxy) - ethyl] -1- (2-hydroxy-ethyl) -3H-imidazol-1 NH 2 O / OH / NO NC X -ium NH 2 / NO N / JX 1- {2 - [(3-Aminopyrazolo [1,5-salt] salt a) pyridin-2-yl) oxy] ethyl) -1-methylpyrrolidinium NH 2 / NO N + 1 / X 1- {2 - [(3-Aminopyrazolo [1,5-a] pyridin-2-yl) oxy] ethyl salt } -1-methylpiperidinium NH2 / NO / \ OX_ 4- {2 - [(3-aminopyrazolo [1,5-a] pyridin-2-yl) oxy] ethyl} -4-methylmorpholin-4-ium NH 2 O salt NON-N + X {2 - [(3-aminopyrazolo [1,5-a] pyridin-2-yl) oxy] ethyl} trimethylammonium salt NH 2 Nu / NX salt of {2 - [(3-aminopyrazol) [1,5-a] pyridin-2-yl) oxy] ethyl} -diisopropyl-methyl-ammonium NH 2 X NN Nui 1- (3-Aminopyrazolo [1,5-a] pyridin-2-yl) salt Methylpyrrolidinium NH 2 N + X-N [1- (3-Amino-pyrazolo [1,5-a] pyridin-2-yl) -pyrrolidin-3-yl] -trimethyl-ammonium salt NH 2 / X 3- (3-Amino-pyrazol [1- [1,5-a] pyridin-2-ylamino) -propyl] -1-methylpiperidinium / NO N- [N + NH 2] n N + N- / N- 4- (3-Amino-pyrazolo [1] salt 5-a] pyridin-2-yl) -1,1-dimethyl-piperazin-1-ium NH 2 X / NH 2 / NO / NN 4- [2- (3-Amino-pyrazolo) salt 5-a] pyridin-2-ylamino) -ethyl] -1,1-dimethyl-piperazin-1-NH2 / X NH NN + N + N + N 4- [2- (3-Amino-pyrazolo) -N 1,5-a] pyridin-2-ylamino) -ethyl] -1-methyl-1-propyl-piperazin-1-naphthalene NH 2 XN NNH 2 OH 4- (3-Amino-pyrazolo [1] 5-a] pyridin-2-yl) -1- (2-hydroxyethyl) piperazin-1-ium NH 2 NH / NON N +. X [4- (3-Amino-pyrazolo [1,5-a] pyridin-2-ylamino) -phenyl] -trimethyl-ammonium salt NH 2 O / NO ~ N ~ x 3- [3- (3- Amino-pyrazolo [1,5-a] pyridin-2-yloxy) -propyl] -1-methyl-3H-imidazol-1-NH2 / N + X- / NO 4- (3-Amino-pyrazolo) salt 1,5-a] pyridin-2-yl) -1,1-dimethyl- [1,4] diazepan-1-lithium NH 2 / NX + salt of [2- (3-Amino-6,7-dimethyl-pyrazolo) [1,5-a] pyridin-2-ylamino) -ethyl] -trimethylammonium NH 4 N- (4-amino-6,7-dimethyl-pyrazolo [1,5-a] pyridin-2-yl) -1,1-dimethyl-piperazin-1-ium NH 2 N N + X- / 4- (3-Amino-6,7-dimethyl-pyrazolo [1,5-a] pyridin salt -2-yl) -1- (2-hydroxy-ethyl) -1-methyl-piperazin-1-ium OH NH 2 + [1- (3-Amino-6,7-dimethyl-pyrazolo a] pyridin-2-yl) -pyrrolidin-3-yl] trimethylammonium N / NH 2 N / JX 1- (3-Amino-6,7-dimethylpyrazolo [1,5-a] pyridin-2-salt) -yl) -1-methylpyrrolidinium [1- (3-Amino-6,7-dimethyl-pyrazolo [1,5-a] pyridin-2-yl) -pyrrolidin-3-yl] (2-hydroxyethyl) salt ) -dimethylammonium NH 2 + X, NùN OH NH 2 {1- [2- (3-Amino-6,7-dimethyl-pyrazolo [1, 5-a] pyridin-2-yloxy) -ethyl] -pyrrolidin-3-yl} -trimethylammonium ~ / NO ~ (X ~ N, NH 2 X 1- {2 - [(3-amino-6) salt, 7-dimethylpyrazolo [1,5-a] pyridin-2-yl) oxy] ethyl] -1-methylpyrrolidinium ~ / NON-NH 2 N- [1- {2 - [(3-amino-6,7-dimethylpyrazolo [ 1,5-a] pyridin-2-yl) oxy] ethyl} -1-methylpiperidinium ~ / NO NH 2 O 4- {2 - [(3-amino-6,7-dimethylpyrazolo [1,5-a]) salt pyridin-2-yl) oxy] ethyl) -4-methylmorpholin-4-yl NH 2, N, N NX {2 - [(3-amino-6,7-dimethylpyrazolo [1,5-a] pyridin-2-yl) salt ) oxy] ethyl} -trimethylammonium NH 2 O ~ / NON ammonium salt {2 - [(3-amino-6,7-dimethylpyrazolo [1,5-a] pyridin-2-yl) oxy] ethyl} -diisopropyl -methyl-NH 2 NH [3- (3-Amino-6,7-dimethyl-pyrazolo [1,5-a] pyridin-2-ylamino) -propyl] -trimethyl-ammonium salt] X NH 2 N-N N ~ salt of [3- (3-Amino-6,7-dimethyl-pyrazolo [1,5-a] pyridin-2-yloxy) -propyl] -trimethyl-ammonium NH 2 O NO 1, X Salt of [3 - (3-Amino-7,8-dihydro-6H-cyclopenta [e] pyrazolo [1,5-a] pyridin-2-yloxy) propyl] trimethylammonium NH 2 N 1 N [(3-amino-7,8-dihyd 6H-cyclopenta [e] pyrazolo [1,5-a] pyridin-2-yl) amino] ethyl] trimethylammonium NH 2 / H 1+ NO N NX Salt of 3 - [(3-amino) 7,8-dihydro-6H-cyclopenta [e] pyrazolo [1,5-a] pyridin-2-yl) amino] propyl} trimethyl ammonium NH 2 / N + N + 1 + X C1N, 1- {2 - [(3-amino-7,8-dihydro-6H-cyclopenta [e] pyrazolo [1,5-a] pyridin-2-yl) amino] ethyl} -3-methyl salt 1H-Imidazol-3-ium NH2 NONH ~ / N` / ~ IN '~ X 1- {3 - [(3-Amino-7,8-dihydro-6H-cyclopenta [e] pyrazolo [1] salt (5-a] pyridin-2-yl) amino] propyl) -3-methyl-1H-imidazol-3-ium NH 2 • N-N-N-N + VX 1- {2 - [(3-amino) -1- 7,8-Dihydro-6H-cyclopenta [e] pyrazolo [1,5-a] pyridin-2-yl) amino] ethyl} -1-methylpyrrolidinium NH 2 HX 1- {2 - [(3-Amino-7) salt 8-Dihydro-6H-cyclopenta [e] pyrazolo [1,5-a] pyridin-2-yl) amino] ethyl} -1-methylpiperidinium NH 2 HNOX 4- {2 - [(3-amino) -4- 7,8-dihydro-6H-cyclopenta [e] pyrazolo [1,5-a] pyridin-2-yl) amino] ethyl} -4-methylmorpholin-4-ium NH 2 / i HX NO N ~~ N Salt of { 2 - [(3-amino-7,8-dihydro-6H-cyclopenta [e] pyrazolo [1,5-a] pyri din-2-yl) amino] ethyl-diisopropyl-methyl-ammonium NH 2 / NO X- [3- (3-Amino-4-dimethylamino-pyrazolo [1,5-a] pyridin-2 salt -ylamino) -propyl] -trimethylammonium NH 2 N.NH 2 / NO 1 X [2- (3-Amino-4-dimethylamino-pyrazolo [1,5-a] pyridin-2-ylamino) -ethyl] salt NN-4- (3-Amino-4-dimethylamino-pyrazolo [1,5-a] pyridin-2-yl) -1-methyl-piperazin-1-ium NN-trimethylammonium salt N / / x NH2NiN [1- (3-Amino-4-dimethylamino-pyrazolo [1,5-a] pyridin-2-yl) -pyrrolidin-3-yl] -trimethylammonium-N-NH2 / salt NO x- Nù 3- [2- (3-Amino-4-dimethylamino-pyrazolo [1,5-a] pyridin-2-yloxy) -ethyl] -1-methyl-3H-imidazol-1-lithium salt N / NH 2 O N + N ~ N *; x- [2- (3-Amino-4-dimethylamino-pyrazolo [1,5-a] pyridin-2-yloxy) -ethyl] -trimethylammonium salt N / x -NH 2 N- / NO / IN {1- [2- (3-Amino-4-dimethylamino-pyrazolo [1,5-a] pyridin-2-yloxy) -ethyl] -pyrrolidin-3-yl} -trimethylammonium salt x NH2 i / NO (3-Amino-2-methanesulfonyl-pyrazolo [1,5-a] pyridin-4-yl) -trimethylammonium salt x NH 2 (3-Amino-2-methoxy-pyrazolo) salt [1,5-a] pyridin-4-yl) -trimethylammonium / NO The nature of the counterion is not critical on the dye power of the compounds of formula (I). When R'1 or R'2 denote a heterocycle, this heterocycle is preferably a cationic heterocycle or a heterocycle substituted with a cationic radical. By way of example, mention may be made of imidazoles substituted with a quaternary ammonium radical or imidazoliums, piperazines substituted with a quaternary ammonium radical or piperaziniums, pyrrolidines substituted with a quaternary ammonium radical or pyrrolidiniums, diazepanes substituted with a quaternary ammonium radical or diazepaniums.

  According to a different embodiment, R'1 or R'2 represent a group ù N + R17R18R19, R17i R18 and R19 being linear or branched C1-C5 alkyls optionally substituted with one or more hydroxyl groups, such as trialkylammonium, tri (hydroxyalkyl) ammonium, hydroxyalkyl-dialkylammonium or di (hydroxyalkyl) alkylammonium. The radicals R'3, R'4 and R'5 independently may be a hydrogen atom, a C1-C4 alkyl radical may be substituted. By way of example, mention may be made of methyl, ethyl, hydroxyethyl, aminoethyl, propyl and butyl radicals. According to a particular embodiment, R'3, R'4 and R'5 independently represent a hydrogen atom or a C1-C4 alkyl radical. According to a particular embodiment, R'4 and R'5 together form a partially saturated or unsaturated 5- or 8-membered ring, in particular an optionally substituted cyclopentene or cyclohexene. According to a particular embodiment, the compound of formula (I ') corresponds to the following formula (I'): Z ~ R'1 R'5 in which Z1i R'1, R'3, R'4 and R ' 5 are as defined above. According to a particular embodiment of this formula, Z1 represents a covalent bond, a radical ## STR1 ## or a radical ## STR2 ## and R '1 is a cationic radical or the bases of oxidation of the invention are generally present each in an amount of between 0.001 to 10% by weight of the total weight of the dyeing composition, preferably between 0.005 and 6%. The dye composition according to the invention contains one or more couplers conventionally used for dyeing keratinous fibers. Among these couplers, there may be mentioned meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts. By way of example of a coupler, mention may be made of 2-methyl-5-aminophenol, 5-N- (3-hydroxyethyl) amino-2-methylphenol, 6-chloro-2-methyl-5-aminophenol, 3-amino phenol, 2,4-dichloro-3-aminophenol, 5-amino-4-chloro-o-cresol, 1,3-dihydroxy benzene, 1,3-dihydroxy-2-methyl benzene, 4-chloro 1,3-dihydroxybenzene, 2,4-

  diamino 1- (β-hydroxyethyloxy) benzene, 2-amino-4- (β-hydroxyethylamino) -1-methoxybenzene, 1,3-diamino benzene, 1,3-bis (2,4-diaminophenoxy) propane, 3-ureido aniline, 3-ureido 1-dimethylamino benzene, sesamol, 1-B-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 1,5-dihydroxy naphthalene, 2,7-naphthalenediol, 1-acetoxy-2-methylnaphthalene, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy N-methylindole, 2-amino-3-hydroxypyridine, 6-hydroxybenzomorpholine 3,5-diamino-2,6-dimethoxypyridine, 2,6-dihydroxy-3-4-dimethylpyridine, 3-amino-2-methylamino-6-methoxypyridine, 1-N- ( B-hydroxyethyl) amino-3,4-methylene dioxybenzene, 2,6-bis- (β-hydroxyethylamino) toluene, 3-methyl-1-phenyl-5-pyrazolone phenyl methyl pyrazolone and their addition salts with a acid. In the composition of the present invention, the coupler or couplers generally represent an amount of between 0.001 and 10% by weight of the total weight of the dyeing composition, preferably between 0.005 and 6%.

  The dye composition of the invention may optionally comprise one or more additional oxidation bases conventionally used for dyeing keratinous fibers, different from the oxidation bases of formula (I). By way of example, these additional oxidation bases may be chosen from para-phenylenediamines other than those previously described, bisphenylalkylenediamines, para-aminophenols, bis-para-aminophenols, ortho-aminophenols, and different heterocyclic bases. oxidation bases of formula (I) and their addition salts. Among the para-phenylenediamines, there may be mentioned, for example, para-phenylenediamine, para-toluenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine and 2,6-dimethyl-para-phenylenediamine. , 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N, N-dimethyl-para-phenylenediamine, N, N-diethyl-para-phenylenediamine, N, N-dipropyl-para-phenylenediamine, 4- amino N, N-diethyl-3-methylaniline, N, N-bis- (13-hydroxyethyl) para-phenylenediamine, 4-N, N-bis- (13-hydroxyethyl) amino-2-methylaniline, 4- N, N-bis- (13-hydroxyethyl) amino-2-chloroaniline, 2-13-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N- (13-hydroxypropyl) para phenylenediamine, 2-hydroxymethyl para-phenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine, N, N- (ethyl, 13-hydroxyethyl) para-phenylenediamine, N- (13, hydroxypropyl) para-phenylenediamine, N- (4'-aminophenyl) para-phenylenediamine, N-phenyl para-phenylenediamine, 2-13-hydroxyethyloxy para-phenylenediamine, 2-13-acetylaminoethyloxy para-phenylenediamine, N-phenylenediamine, (R-Methoxyethyl) para-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl para-phenylenediamine, 2-hydroxyethylamino-5-amino toluene, 3-hydroxy-1- (4'-aminophenyl) pyrrolidine and their salts addition with an acid. Among the para-phenylenediamines mentioned above, para-phenylenediamine, para-toluenediamine, 2-isopropyl para-phenylenediamine, 2-13-hydroxyethyl paraphenylenediamine, 2-13-hydroxyethyloxy para-phenylenediamine, 2 6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N, N-bis- (13-hydroxyethyl) para-phenylenediamine, 2-chloro-para-phenylenediamine, 2-13-acetylaminoethyloxy para-phenylenediamine, and their addition salts with an acid are particularly preferred. Among the bis-phenylalkylenediamines, mention may be made, by way of example, of N, N'-bis- (13-hydroxyethyl) N, N'-bis- (4'-aminophenyl) 1,3-diamino propanol, N N, N'-bis- (13-hydroxyethyl) N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- ( 13-hydroxyethyl) N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis- (4-methylaminophenyl) tetramethylenediamine, N, N'-bis (ethyl) N, N ' -bis- (4'-amino, 3'-methylphenyl) ethylenediamine, 1,8-bis (2,5-diamino phenoxy) -3,6-dioxaoctane, and their addition salts with an acid. Among para-aminophenols, para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluoro phenol, 4-amino-3-hydroxymethylphenol, 4-amino-2 are exemplified. methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (13-hydroxyethylaminomethyl) phenol, 4-amino-2 fluoro phenol, 1-hydroxy-4-methylamino-benzene, 2-2'-methylenebis-4-amino phenol and their addition salts with an acid.

  Among the ortho-aminophenols, mention may be made, for example, of 2-amino phenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-aminophenol, and their addition salts with an acid. Among the heterocyclic bases that may be mentioned by way of example are pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.

  Among the pyridine derivatives, mention may be made of the compounds described for example in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino pyridine, 2- (4-methoxyphenyl) amino-3-amino pyridine, 2,3-diamino-6-methoxy pyridine, 2- (R-methoxyethyl) amino-3-amino-6-methoxy pyridine, 3,4-diamino pyridine, and their addition salts with an acid.

  Among the pyrimidine derivatives, mention may be made of the compounds described, for example, in DE 2359399; JP 88-169571; JP 05-63124; EP 0770375 or patent application WO 96/15765 such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine, , 4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and pyrazolopyrimidine derivatives such as those mentioned in the patent application FR-A-2750048 and among which mention may be made of pyrazolo [1, 5-a] -pyrimidine-3,7-diamine; 2,5-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine; pyrazolo [1,5-a] pyrimidine-3,5-diamine; 2,7-dimethyl pyrazolo [1,5-a] pyrimidine-3,5-diamine; 3-amino pyrazolo [1,5-a] pyrimidin-7-ol; 3-amino pyrazolo [1,5-a] pyrimidin-5-ol; 2- (3-amino pyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol, 2- (7-amino pyrazolo [1,5-a] pyrimidin-3-ylamino) - ethanol, 2 - [(3-amino-pyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol, 2 - [(7-amino-pyrazolo [ 1,5-a] pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol, 5,6-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine, 2,6-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine, 2,5-N, 7-N-7-tetramethyl-pyrazolo [1,5-a] -pyrimidine-3, 7-diamine, 3-amino-5-methyl-7-imidazolylpropylamino pyrazolo [1,5-a] pyrimidine and their acid addition salts and their tautomeric forms, when tautomeric equilibrium exists.

  Among the pyrazole derivatives, mention may be made of the compounds described in DE 3843892, DE 4133957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988 as the 4.5 amino-methyl pyrazole, 4,5-diamino-1-yl-hydroxyethyl) pyrazole, 3,4-diamino pyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 4,5-diamino diamino 1,3-dimethyl pyrazole, 4,5-diamino-3-methyl-1-phenyl pyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazino pyrazole, 1-Benzyl-4,5-diamino-3-methyl-pyrazole, 4,5-diamino-3-tert-butyl-1-methyl-pyrazole, 4,5-diamino-1-tert-butyl-3-methyl-pyrazole, 4,5 1-methyl-3-methyl pyrazole, 4,5-diamino-1-ethyl-3-methyl pyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole, 4,5 1-diamino-ethyl 3-hydroxymethyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-methyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropyl pyrazole, 4,5-diamino-3-methyl 1-isopropyl pyrazole, 4-amino 5- (2'-aminoethyl) amino 1,3-dimethyl pyrazole, 3,4,5-triamino pyrazole, 1-methyl 3,4,5-triamino pyrazole, 3,5-diamino-1-methyl-4-methylamino pyrazole, 3,5-diamino-4-β-hydroxyethyl) amino-1-methyl pyrazole, and their addition salts with an acid. There may also be mentioned diaminopyrazolinones described in the patent application FR2886137 and in particular 2,3-diamino-6,7-dihydro1H, 5H-pyrazol-1-one and its salts. In general, the addition salts of the oxidation bases and couplers that can be used in the context of the invention are chosen especially from the addition salts with an acid such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates and addition salts with a base such as sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines. The dye composition in accordance with the invention may also contain one or more direct dyes that may be chosen in particular from nitro dyes of the benzene series, azo direct dyes and methine direct dyes. These direct dyes may be nonionic, anionic or cationic in nature. The composition according to the invention also comprises one or more surfactants chosen from (C 8 -C 30) alkylcarboxylic acids and their salts, (C 12 -C 20) alkyl polyglucosides and mono or polyglycerolated surfactants. More particularly, the alkyl ether carboxylic acid (s) and their salts are chosen from compounds of the following formula (II):

  Wherein R8 represents a linear or branched C8-C22 alkyl or alkylene radical, a (C8-C9) alkyl radical, such as a (C8-C9) alkyl radical, or R8 represents a linear or branched C8-C22 alkyl or alkylene radical; phenyl; A represents an oxygen atom or a group -CO-, -NH- or -CO-O-; B is constituted of a random sequence or blocks of p 'units -C3H60- and n' units -C2H40-; n 'is an integer from 1 to 30; p 'is an integer from 0 to 15; q 'is an integer equal to 0 or 1; X 'denotes a hydrogen atom or else Na, K, Li, Y 2 Mg or a monoethanolamine, ammonium or triethanolamine residue.

  According to a particular embodiment of the invention, the alkyl ether carboxylic acids and their salts are chosen from those of formula (II) in which R8 denotes a C8-C22 alkyl radical, preferably C10-C18, A represents a oxygen atom, X 'denotes a hydrogen or sodium atom, p' = 0, n 'ranges from 1 to 20, and preferably 1 to 10, and q' is equal to 0 or 1.

  The commercial products may consist of a mixture of the alkyl ether carboxylic acids or their salts, and in this case it is the average of the values of n 'or of p' which are indicated. Among the commercial products, it is possible to use, preferably, the products sold by CHEM Y under the names AKYPO NP 70 (R 8 = nonylphenyl, A = 0, n '= 7, p' = 0, q '= 1, X '= H); AKYPO NP 40 (R 8 = nonylphenyl, A = 0, n '= 4, p' = 0, q '= 1, X' = H); AKYPO OP 40 (R 8 = octylphenyl, A = 0, n '= 4, p' = 0, q '= 1, X' = H); AKYPO OP 80 (R 8 = octylphenyl, A = O, n '= 8, p' = 0, q '= 1, X' = H); AKYPO OP 190 (R 8 = octylphenyl, A = O, n '= 19, p' = 0, q '= 1, X' = H); AKYPO RLM 38 (R8 = alkyl (C12-C14), A = O, average number = 3.8, p '= 0, q' = 1, X '= H), AKYPO RLM 38 NV (R8 = alkyl) (C12-C14), A = O, n '= 4, p' = 0, q '= 1, X' = Na); AKYPO RLM 45 (R8 = (C12-C14) alkyl, A = O, n = 4.5, p '= 0, q' = 1, X '= H); AKYPO RLM 45 NV (R8 = C12-C14 alkyl, A = O, n = 4.5 average, p '= 0, q' = 1, X '= Na); AKYPO RLM 100 (R8 = C12-C14 alkyl, A = O, n '= 10, p' = 0, q '= 1, X' = H); AKYPO RLM 100 NV (R8 = C12-C14 alkyl, A = O, n '= 10, p' = 0, q '= 1, X' = Na); AKYPO RLM 130 (R8 = C12-C14 alkyl, A = O, n '= 13, p' = 0, q '= 1, X' = H); AKYPO RLM 160 NV (R8 = C12-C14 alkyl, A = O, n '= 16, p' = 0, q '= 1, X' = Na); AKYPO RS 60 (R8 = alkyl (C17), A = -CO-O-, n '= 6, p' = 0, q '= 1, X' = H); AKYPO SCR 60 (R8 = cetyl, A = O / R8 = alkyl (C17), A = -CO-O-; n '= 6, p' = 0, q '= 1, X' = H); AKYPO RS 100 (R8-A = stearyl, n '= 10, p' = 0, q '= 1, X' = H); AKYPO RO 50 (R8-A = oleyl, n '= 5, p' = 0, q '= 1, X' = H); AKYPO SOFT 70 NV; AKYPO SOFT 45 NV; AKYPO SOFT 100 NV; AKYPO RLM 45 CA; AKYPO RLM 70; AKYPO TFC; AKYPO FOM (R8 = lauryl, A = NH); AKYPO SURFINE WLL; or by SANDOZ under the names: SANDOPAN ACA-48 (R8 = cetyl, A = O / alkyl (C17), A = -CO-O-; n '= 24, p' = 0, q '= 1, X '= H); SANDOPAN DTC-Acid (R8 = alkyl (C13), A = O, n '= 6, p' = 0, q '= 1, X' = H); SANDOPAN DTC (R8 = alkyl (C13), A = O, n '= 6, p' = 0, q '= 1, X' = Na); SANDOPAN LS 24 (R8 = C12-C14 alkyl, A = O, n '= 12, p' = 0, q '= 1, X' = Na); SANDOPAN JA 36 (R8 = alkyl (C13), A = O, n '= 18, p' = 0, q '= 1, X' = H). The alkyl polyglycoside (s) are well known and may be more particularly represented by the following general formula: R 9 O- (R 10 O) y- (G) - (III) in which R 9 represents a linear or branched alkyl and / or alkylene radical having about from 12 to 30 carbon atoms, an alkylphenyl radical in which the linear or branched alkyl radical contains from 12 to 30 carbon atoms, Rio represents one or more alkylene radicals comprising approximately 2 to 4 carbon atoms, G represents a sugar unit comprising from 5 to 6 carbon atoms, t 'denotes a value ranging from 0 to 10, preferably 0 to 4, and v denotes a value ranging from 1 to 15. Preferred alkyl polyglycosides according to the present invention are compounds of formula ( III) in which R 9 more particularly denotes a saturated or unsaturated, linear or branched alkyl radical containing from 12 to 30 carbon atoms, t 'denotes a value ranging from 0 to 3 and more particularly still even 0, G may denote glucose, fructose or galactose, preferably glucose. The degree of polymerization, ie the value of v in formula (III), can range from 1 to 15, preferably from 1 to 4. The average degree of polymerization is more particularly between 1 and 2 and even more preferably from 1 to , 1 to 1.5. The glycosidic linkages between the sugar units are of the 1-6 or 1-4 type and preferably 1-4. Compounds of formula (III) are especially represented by the products sold by the company COGNIS under the names PLANTAREN (600 CS / U, 1200 and 1300) or PLANTACARE (818 and 1200). The mono- or polyglycerolated surfactant or surfactants preferably comprise, on average, from 1 to 30 glycerol groups, more particularly from 1 to 10 glycerol groups and in particular from 1.5 to 5. The monoglycerolated or polyglycerolated surfactant (s) are preferably chosen among the compounds of the following formulas: RäO [CH 2 CH (CH 2 OH) O] mH; RäO [CH₂CH (OH) CH₂O] mH or RäO [CH (CH₂OH) CH₂O] mH; wherein R a represents a saturated or unsaturated hydrocarbon radical, linear or branched, having from 8 to 40 carbon atoms and preferably from 10 to 30 carbon atoms; m is a number between 1 and 30, preferably between 1 and 10, more preferably from 1.5 to 6. Rä may optionally include heteroatoms such as for example oxygen and nitrogen. In particular, R may optionally comprise one or more hydroxy and / or ether and / or amide groups. R a preferably denotes a C 10 -C 20 alkyl or alkylene radical, optionally mono or polyhydroxylated. For example, the polyglycerolated hydroxylaurylether (3.5 moles) sold under the name Chimexane NF from Chimex can be used.

  Preferably, the surfactant (s) useful in the context of the present invention are chosen from lauryl ether carboxylic acid, (C 12 -C 14 / C 16 68/26/6 alkyl) polyglucoside and polyglycerolated cetearyl alcohol with r moles glycerol, r being an integer between 2 and 10, preferably between 2 and 6.

  The above surfactant (s) are each present in the composition according to the invention in an amount of between 0.01% and 30% by weight, preferably between 0.1% and 15% by weight relative to the total weight of the composition. dye composition. The medium suitable for dyeing keratinous fibers, in particular human fibers such as the hair, also called dyeing medium, generally comprises water or a mixture of water and at least one organic solvent for solubilizing the compounds which do not would not be sufficiently soluble in water. As organic solvent, there may be mentioned for example lower alkanols C1-C4, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof. The solvents are preferably present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 30% by weight approximately. The dye composition in accordance with the invention may also contain various adjuvants conventionally used in compositions for dyeing hair, such as anionic, cationic, amphoteric and nonionic surfactants other than those of the invention, anionic, cationic polymers, nonionic, amphoteric, zwitterionic or mixtures thereof, inorganic or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example, volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preserving agents, opacifying agents. The adjuvants above are generally present in an amount for each of them between 0.01 and 20% by weight relative to the weight of the composition. Of course, one skilled in the art will take care to choose this or these optional additional compounds such that the advantageous properties intrinsically attached to the oxidation dyeing composition according to the invention are not, or not substantially impaired by the addition or additions envisaged.

  The pH of the dye composition according to the invention is generally between 3 and 12 approximately, and preferably between 5 and 11 approximately. It can be adjusted to the desired value by means of acidifying or alkalizing agents usually used for dyeing keratin fibers or else using conventional buffer systems. Among the acidifying agents, mention may be made, by way of example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulphonic acids.

  Among the alkalinizing agents that may be mentioned, by way of example, are ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and following formula (IV): Ra \ R bi NW-NR ~ R d (IV) wherein W is a propylene residue optionally substituted with a hydroxyl group or a C1-C4 alkyl radical; Ra, Rb, R, and Rd, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 hydroxyalkyl radical.

  The dye composition according to the invention may be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratinous fibers, and especially human hair. The process of the present invention is a process in which the composition according to the present invention as defined above is applied to the fibers in the presence of an oxidizing agent for a time sufficient to develop the desired coloration. The color can be revealed at acidic, neutral or alkaline pH and the oxidizing agent can be added to the composition of the invention just at the time of use or it can be used from an oxidizing composition containing it applied simultaneously or sequentially to the composition of the invention. The revelation at acidic pH may be particularly interesting. According to a particular embodiment, the composition according to the present invention is mixed, preferably at the time of use, with a composition containing, in a medium suitable for dyeing, at least one oxidizing agent, this oxidizing agent being present in an amount sufficient to develop a coloration. The mixture obtained is then applied to the keratinous fibers. After a residence time of about 3 to 50 minutes, preferably about 5 to 30 minutes, the keratinous fibers are rinsed, washed with shampoo, rinsed again and then dried. The oxidizing agents conventionally used for the oxidation dyeing of keratin fibers are, for example, hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids and oxidase enzymes. among which there may be mentioned peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases. Hydrogen peroxide is particularly preferred. The oxidizing composition may also contain various adjuvants conventionally used in compositions for dyeing hair and as defined above. The pH of the oxidizing composition containing the oxidizing agent is such that, after mixing with the dyeing composition, the pH of the resulting composition applied to the keratinous fibers preferably varies between 3 and 12 approximately, and even more preferably between 5 and 11. It can be adjusted to the desired value by means of acidifying or basifying agents usually used for dyeing keratinous fibers and as defined above. The ready-to-use composition which is finally applied to the keratin fibers may be in various forms, such as in the form of liquids, creams, gels or in any other form suitable for dyeing keratinous fibers, and including human hair. The invention also relates to a multi-compartment device or "kit" of dyeing in which a first compartment contains the dye composition of the present invention defined above and a second compartment contains an oxidizing agent. This device may be equipped with means for delivering the desired mixture to the hair, such as the devices described in patent FR-2 586 913 in the name of the applicant. From this device, it is possible to dye the keratinous fibers from a process which comprises mixing a dyeing composition comprising one or more oxidation bases of formula (I), one or more couplers and one or more several surfactants according to the invention with an oxidizing agent, and the application of the mixture obtained on the keratinous fibers for a time sufficient to develop the desired coloration. The examples which follow serve to illustrate the invention without, however, being limiting in nature.

Examples Composition 1

  Composition 1 comprises the following dyes: 2 - [(3-aminopyrazolo [1,5-a] pyridin-2-yl) oxy] ethanol hydrochloride 0.006 moles per 100 g 1-Methyl-2-hydroxy-4-aminobenzene 0.006 mole per 100 q introduced in the following medium:

  Carboxylic lauryl ether acid 4.5 EO 7.0 g (Akypo RLM 45 sold by CHEM Y) Lauryl alcohol 2 EO (Dehydol LS-2-DEO-N sold by COGNIS 4.0 g Decyl alcohol 5 EO 8.0 g (Empilan KA-5/90 FL sold by ALBRIGHT & WILSON) Oleyl alcohol 3.0 g Monoethanolamide of acyl acid (C13 / 015) carboxylic ether with 25 g moles of ethylene oxide Cationic associative polymer (Quatrisoft LM 2008 sold by 1.0 g AMERCHOL) Monoethanolamine 2 0 g Polyquaternium 6 (Merquat 8 100 sold by CALGON) 1.5 g Ethanol 11 g Propylene glycol 5.0 g Dipropylene glycol 5.0 g Reducing agents, antioxidants qs

  Sequestering q.s. Perfume q.s. Ammonia (at 20.5% NH 3) 1.6 Demineralized water QSP 100 g Composition 2 Composition 2 comprises the following dyes: 2 - [(3-aminopyrazolo [1,5-a] pyridin-2 -0.008 mole chloride hydrochloride % yl) amino] -N, N, N-trimethylethanaminium 2-chloro-6-methyl-3-aminophenol 0.008 mol 0/0 introduced into the following medium:

  Alkyl (C8 / C, o 50/50) polyglucoside (2) in 60% aqueous solution 7.0 g MA * Lauryl alcohol 2 EO (Dehydol LS-2-DEO-N sold by COGNIS 4.0 g 10 decyl alcohol 5 EO 8.0 g (Empilan KA-5/90-FL sold by ALBRIGHT & WILSON) Oleyl alcohol 3.0 g Monoethanolamide of akyl acid (013/015) carboxylic ether with 5 g 2 moles of ethylene oxide Cationic associative polymer (Quatrisoft LM 2008 sold by 1.0 g AMERCHOL) Monoethanolamine 2.0 g Polyquaternium 6 (Merquat 8 100 sold by CALGON) 1.5 g Ethanol 11.0 g 20 Propylene glycol 5.0 g Dipropylene glycol 5.0 g Reducing agents, antioxidants qs Sequestering qs Fragrance qs 25 Ammonia (at 20.5% in NH3) 1.6 Demineralized water qs 100 g

  MA * means that the content is indicated in grams of active ingredient. Composition 3 Composition 3 comprises the following dyes: 2 - [(3-aminopyrazolo [1,5-a] pyridin-2 -0.007 mole% yl) amino] -N, N, N-trimethylethanaminium chloride chloride hydrochloride aminophenol 0.007 mol 0/0 introduced into the following medium:

  Mixtures of C18 to C24 linear alcohols [C18 / 020/022/024, 3 g 7/58/30/6, alcohol contents> 95%] (NAFOL 20-22) Linear C18 to C18 alcohols mixtures C24 1.35 g [C18 / 020/022/024 7/58/30/6, contents of alcohols> 95%] polyglycerolated with 6 moles of glycerol Cetyl alcohol polyglycerolated with 2 moles of glycerol 4.0 g Cetearyl alcohol polyglycerolated with 6 moles of glycerol 2.0 g Oleic acid 2.6 g Glycol distearate 2.0 g Propylene glycol 7.5 g Coproacion acid monohydroamide 2.0 g Aculyn 44 sold by Rohm & Haas 1.4 g MA * 20 Crosslinked polyacrylic acid 0.6 g Cationic polymer of formula (W) 3 g MA Merquat 100 sold by the company CALGON 0.4 g MA Reducers 0.7g Sequestering agents 0.2 g 25 Pure monoethanolamine 1.06 g Ammonia (at 20.5% NH 3) 11.1 g Water QSP 100 g

  MA * means that the content is indicated in grams of active ingredient. 275 Mode of application

  Each composition is diluted extemporaneously with 1.5 times its weight of hydrogen peroxide at 20 volumes and whose pH is 3. The mixture thus produced is applied to natural gray hair at 90% white, at a rate of 30 g for 3 g of hair for 30 minutes. The hair is then rinsed, washed with standard shampoo and dried.

Results

  Capillary staining is evaluated visually. Height of tone Reflection Composition 1 Dark Blonde Red slightly purplish Composition 2 Dark Blonde Purplish Blue Composition 3 Blond Blue Ash 28 These shades are stubborn and uniform

Claims (27)

  1. dye composition comprising, in a dyeing medium suitable for dyeing keratin fibers, • one or more aminopyrazolopyridine oxidation bases of formula (I) below: R 'Z 2 NH 2 Z ~ R' 1 (I) R ' Wherein X 1 and Z 2 independently represent a single covalent bond, a divalent radical selected from --O (CH 2) p -, where p denotes an integer ranging from 0 to 6 - a radical CH 2) q (C 6 H 4) t q, q denoting an integer ranging from 0 to 6 and t denoting 0 or 1. R '6 represents a hydrogen atom, a C1-C6 alkyl radical optionally substituted with one or more hydroxyl groups . Z1 can also represent a divalent radical ùS-, -SO-, -SO2- when R'1 is a methyl radical, R'1 and R'2 independently represent: - a hydrogen - a C1-C10 alkyl radical, optionally substituted and optionally interrupted by a heteroatom or a group selected from O, N, Si, S, SO, SO 2, a halogen, a SO 3 H radical, a 5 to 8-membered ring, substituted or unsubstituted, saturated, unsaturated or aromatic, optionally containing one or more heteroatoms or groups selected from N, O, S, SO2i -CO-, the ring may be cationic and / or substituted with a cationic radical, a group -N + R17R18R19, R17i R13 and R19 being linear or branched C 1 -C 5 alkyl optionally substituted with one or more hydroxyl groups. When Z, respectively Z2 represents a covalent bond, then R ', respectively R'2 may also represent a radical: - C, -C6 alkylcarbonyl, optionally substituted - -O-00-R, ùCO-OR, NR-CO- R 'or CO-NRR' in which R and R 'independently represent a hydrogen atom or an optionally substituted C1-C6 alkyl radical, • R'3, R'4 and R'5, which are identical or different, represent - a hydrogen atom; a hydroxyl radical; a C1-C6 alkoxy radical; a C1-C6 alkylthio radical; an amino radical; a monoalkylamino radical; and a C1-C6 dialkylamino radical in which the radicals alkyls can form, with the nitrogen atom to which they are attached, a 5- to 8-membered saturated or unsaturated heterocycle, aromatic or otherwise, which may contain one or more heteroatoms or groups chosen from N, O, S and SO2i CO, l heterocycle which may be cationic, and / or substituted by a cationic radical, an alkylcarbonyl radical C1-C6, optionally substituted, a radical -O-00-R, -CCO-OR, NR-CO-R 'or CO-NRR' with R and R 'as defined above, - a halogen, a radical - NHSO3H, - an optionally substituted C1-C4 alkyl radical, - a saturated, unsaturated or aromatic carbon ring, optionally substituted. R'3, R'4 and R'5 may form, two by two, a saturated or unsaturated ring; X represents an ion or group of ions making it possible to ensure the electronegativity of the derivative of formula (I), with the condition that at least one of the groups R ', and R'2 represents a cationic radical. One or more couplers; and one or more surfactants selected from (C 8 -C 30) alkyl carboxylic ether acids and their salts, (C 12 -C 30) alkyl polyglucosides and mono or polyglycerolated surfactants. 10 15 20 25 30   2. Composition according to claim 1, characterized in that, in the formula (I), Z and / or Z2 represents a covalent bond, a radical ## STR5 ## or a radical ## STR2 ## and / or R'2 is a cationic radical.   3. The composition according to claim 2, in which R 'and / or R'2 denote quaternary ammonium-substituted imidazoles or imidazoliums, quaternary ammonium-substituted piperazines or piperaziniums, ammonium-substituted pyrrolidines. or pyrrolidiniums, diazepanes substituted with a quaternary ammonium radical or diazepaniums.   4. Composition according to claim 1, wherein R 'and / or R'2 independently represent a hydrogen atom, or a trialkylammonium, tri (hydroxyalkyl) ammonium, hydroxyalkyl-dialkylammonium or di (hydroxyalkyl) alkylammonium group. .   5. Composition according to any one of the preceding claims wherein the radicals R'3, R'4 and R'5 independently represent a hydrogen atom, a C1-C4 alkyl radical may be substituted.   6. Composition according to any one of the preceding claims wherein the compound of formula (I) corresponds to the following formula (I '): NH 2 Z ~ R' 1 R '5 wherein Z ,, R'1, R' 3, R'4 and R'5 are as defined in any one of the preceding claims.   7. A composition according to claim 6 wherein Z, is a covalent bond, a radical NR1 (CH2) q or a radical O (CH2) q and R 'is a cationic radical.   8. The composition according to claim 1, wherein the compound of formula (I) is chosen from: a) pyridin-2-ylamino) -ethyl] -trimethylammonium N-NH 2 N- [3- (3-Amino-pyrazolo [1,5-a] pyridin-2-yl) -1-methyl-3H salt imidazol-1-NH 2 NH 2 / NO X +, / - N 2 - [2- (3-Amino-pyrazolo [1,5-a] pyridin-2-ylamino) -ethyl] -ethyl-dimethyl-ammonium salt NH2 4NH / NO X + OH [2- (3-Amino-pyrazolo [1,5-a] pyridin-2-ylamino) -ethyl] - (2-hydroxy-ethyl) -dimethyl-ammonium NH 2 salt 3- (3-Amino-pyrazolo [1,5-a] pyridin-2-ylamino) -propyl] -trimethylammonium / NO ~ I N + x -NH 2 [4- (3-Amino-pyrazolo [1] salt, 5-a] pyridin-2-ylamino) -butyl] -trimethylammonium NH 2 + NH 2 / NH 2 / NON X N + [5- (3-Amino-pyrazolo [1,5-a] pyridin] salt 2-ylamino) -pentyl] -trimethylammonium NH 2 NH / NON- / --- '-% - NXN 3- [2- (3-Amino-pyrazolo [1,5-a] pyridin-2-ylamino salt ) -ethyl] -1-methyl-3H-imidazol-1-lithium NH2 / NO N ~ + / X 3- [3- (3-Amino-pyrazolo [1,5-a] pyryl salt 2-ylamino) -propyl] -1-methyl-3H-imidazol-1-ium NH 2 / NO 3 NH 3 / N-N-OH-NX 3- [3- 3-Amino-pyrazolo [1,5-a] pyridin-2-ylamino) -propyl] -1 (2-hydroxy-ethyl) -3H-imidazol-1-ammonium NH2 3- [2- (3-Amino) salt pyrazolo [1,5-a] pyridin-2-yloxy) -ethyl] -1- (2-hydroxy-ethyl) -3H-imidazol-1 O / -OH / NO ~ N ~ X -ium NH 2 / NO N 1- {2 - [(3-Aminopyrazolo [1,5-a] pyridin-2-yl) oxy] ethyl} -1-methylpyrrolidinium salt / NH 2 / NO N '/ 1 / X Salt of 1- {2- [ (3-Aminopyrazolo [1,5-a] pyridin-2-yl) oxy] ethyl-1-methylpiperidinium-NH, N-butyl 4- {2 - [(3-aminopyrazolo [1,5-a]) salt ] pyridin-2-yl) oxy] ethyl) -4-methylmorpholin-4-ium NH2 O1 / NO N + / \ X {2 - [(3-aminopyrazolo [1,5-a] pyridin-2-yl) salt ) oxy] ethyl} trimethyl ammonium NH2 / NO ~ N + X- {2 - [(3-Aminopyrazolo [1,5-a] pyridin-2-yl) oxy] ethyl} -diisopropyl-methyl-ammonium NH2 salt X- / / NO Nui 1- (3-aminopyrazolo [1,5-a] pyridin-2-yl) -1-methylpyrrolidinium salt NH2 + / NO N1 NX [1- (3-Amino-pyrazolo) salt [1,5-a] pyridin-2-yl) -pyrrolidin-3-yl] trimethyl-ammonia ## STR1 ## 1- [3- (3-Amino-pyrazolo [1,5-a] pyridin-2-ylamino) -propyl] -1-methylpiperidinium salt NH 2 -Amino-pyrazolo [1,5-a] pyridin-2-yl) -1,1-dimethyl-piperazin-1-ium / ù X / NO N \ / NH₂ NH / + / NO / - NN 4- [2- (3-Amino-pyrazolo [1,5-a] pyridin-2-ylamino) -ethyl] -1,1-dimethyl-piperazin-1-iumNH 2 / X / NH 4- [2- (3-Amino-pyrazolo [1,5-a] pyridin-2-ylamino) -ethyl] -1-methyl-1-propyl-piperazin-1-NH 2 N 2 4- (3-Amino-pyrazolo [1,5-a] pyridin-2-yl) -1- (2-hydroxy-ethyl) -piperazin-1-ammonium NH 2 NH 4 -alkyl NO N + • X [4- (3-Amino-pyrazolo [1,5-a] pyridin-2-ylamino) -phenyl] -trimethyl-ammonium salt NH 2 O / NO ~ + / XN ~ -ium salt of 3- [3- (3-Amino-pyrazolo [1,5-a] pyridin-2-yloxy) -propyl] -1-methyl-3H-imidazol-1 NH 2 / NO N + X- -ium 4- (3-salt) -Amino-pyrazolo [1,5-a] pyridin-2-yl) -1,1-dimethyl- [1,4] diazepan-1NH 2 / NX + salt of [2- (3-Amino-6,7- dimethyl-pyrazolo [1,5-a] pyridin-2-ylamino) -ethyl] -trimethylammonium NH 2 / ù / + X ~ / N 4- (3-Amino) salt 6,7-dimethyl-pyrazolo [1,5-a] pyridin-2-yl) -1,1-dimethyl-piperazin-1-naphthon N N + X- / 4- (3-Amino-6) salt; 7-dimethyl-pyrazolo [1,5-a] pyridin-2-yl) -1- (2-hydroxy-ethyl) -1-methyl-piperazin-1-ium OH NH 2 + [1- (3-Amino) salt 6,7-dimethyl-pyrazolo [1,5-a] pyridin-2-yl) -pyrrolidin-3-yl] -trimethylammonium, N, N X / NH 2 NJ X 1- (3-Amino-6) salt, 7-dimethylpyrazolo [1,5-a] pyridin-2-yl) -1-methylpyrrolidinium [1- (3-Amino-6,7-dimethyl-pyrazolo [1,5-a] pyridin-2-yl) salt pyrrolidin-3-yl] (2-hydroxyethyl) -dimethylammonium NH 2 + X OH NH 2, N, N- {1- [2- (3-Amino-6,7-dimethyl-pyrazolo) salt; a] pyridin-2-yloxy) -ethyl] -pyrrolidin-3-yl} -trimethylammonium-N-, NH 2 / NOX 1- {2 - [(3-amino-6,7-dimethylpyrazolo [1 5-a] pyridin-2-yl) oxy] ethyl] -1-methylpyrrolidinium ~ / NON-NH 2 X 1- {2 - [(3-Amino-6,7-dimethylpyrazolo [1,5-a] pyridine) salt 2-yl) oxy] ethyl} -1-methylpiperidinium NH2NiNN + 4- {2 - [(3-amino-6,7-dimethylpyrazolo [1,5-a] pyridin-2-yl) oxy] ethyl salt -4-methylmorpholin-4-ium ~ / NON NH2 NX Salt of {2} - [(3-amino-6,7-dimethylpyrazolo [1,5-a] pyridin-2-yl) oxy] ethyl] trimethylammonium methyl ammonium salt NH 2 {2 - [(3-amino-6, 7-dimethylpyrazolo [1,5-a] pyridin-2-yl) oxy] ethyl] -diisopropyl-NH 2 NH N + N + x [3- (3-Amino-6,7-dimethyl-pyrazolo [1] salt, 5-a] pyridin-2-ylamino) propyl] trimethylammonium NH 4 O N N + x- [3- (3-Amino-6,7-dimethyl-pyrazolo [1,5-a] pyridine) salt 2-yloxy) -propyl] -trimethylammonium NH, ON, N, + X [3- (3-Amino-7,8-dihydro-6H-cyclopenta [e] pyrazolo [1,5-a] salt] ] pyridin-2-yloxy) -propyl] -trimethylammonium NH 2 N-N + N-N 1 Salt of {2 - [(3-amino-7,8-dihydro-6H-cyclopenta [e] pyrazolo [ 1,5-a] pyridin-2-yl) amino] ethyl] -trimethylammonium NH 2 / H + N + N N-1 X Salt of {3 - [(3-amino-7,8-dihydro-6H) cyclopenta [e] pyrazolo [1,5-a] pyridin-2-yl) amino] propyl} -trimethylammonium NH 2/1 HN NO 1 / w 1 + X CH 2, Salt of 1- {2 - [(3-amino-7,8-dihydro-6H-cyclopenta [e] pyrazolo [1,5-a] pyridin-2-yl) amino] ethyl) -3-methyl-1H-imidazol-3-ium NH2 N ~ / N` / ~ IN '~ NO _ X Salt of 1- {3 - [( 3-amino-7,8-dihydro-6H-cyclopenta [e] pyrazolo [1,5-a] pyridin-2-yl) amino] propyl} -3-methyl-1H-imidazol-3-ium NH 2 H / NNI + ~ N \ NVX 1- {2 - [(3-amino-7,8-dihydro-6H-cyclopenta [e] pyrazolo [1,5-a] pyridin-2-yl) amino] ethyl} -1 salt Methylpyrrolidinium NH 2 N + NON ~ \ NX 1- {2 - [(3-amino-7,8-dihydro-6H-cyclopenta [e] pyrazolo [1,5-a] pyridin-2-yl) amino salt] ethyl} -1-methylpiperidinium NH 2 / i H NO N \ / \ N ~~ X 4- {2 - [(3-Amino-7,8-dihydro-6H-cyclopenta [e] pyrazolo [1,5- a] pyridin-2-yl) amino] ethyl} -4-methylmorpholin-4-ium NH 2 X {2 - [(3-Amino-7,8-dihydro-6H-cyclopenta [e] pyrazolo [1,5-salt] salt α-pyridin-2-yl) amino] ethyl} -diisopropyl-methyl-ammonium NH 2 NH NùN N + X- [3- (3-Amino-4-dimethylamino-pyrazolo [1,5-a] pyridin-2 salt -ylamino) -propyl] -trimethylammonium NH2NHNNNN 1 x [2- (3-Amino-4-dimethylamino-pyrazolo [1,5-a] pyridin-2-ylamino) -ethyl] -trimethyl salt 4- (3-Amino-4-dimethylamino-pyrazolo [1,5-a] pyridin-2-yl) -1-methyl-piperazin-1 / NO 2 -ammonium salt ium salt of [1- (3-amino) 4-dimethylamino-pyrazolo [1,5-a] pyridin-2-yl) -pyrrolidin-3-yl] -trimethylammonium N / NH 2 / NOXN / NH 2 / NOX-N 3- [3- 2- (3-Amino-4-dimethylamino-pyrazolo [1,5-a] pyridin-2-yloxy) -ethyl] -1-methyl-3H-imidazol-1-lithium salt of [2- (3-Amino-4) -Dimethylamino-pyrazolo [1,5-a] pyridin-2-yloxy) -ethyl] -trimethylammonium-N-NH 2 O / NO-N + - IX N / X-NH 2 N-N Salt of {1- [2- (3-Amino-4-dimethylamino-pyrazolo [1,5-a] pyridin-2-yloxy) -ethyl] -pyrrolidin-3-yl} -trimethyl-ammonium X NH 2 - / NO (3-Amino-2-methanesulfonyl-pyrazolo [1,5-a] pyridin-4-yl) -trimethylammonium salt x-NH 2 (3-Amino-2-methoxy-pyrazolo [1] salt , 5-a] pyridin-4-yl) trimethylammonium / NO   9. Composition according to any one of the preceding claims, characterized in that the content of compound of formula (I) is between 0.001 to 10% by weight of the total weight of the dye composition.   10. Composition according to any one of the preceding claims, characterized in that the coupler or couplers are chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts.   11. The composition of claim 10, characterized in that the amount of each of the couplers is between 0.001 and 10% by weight of the total weight of the dye composition. 15   12. Composition according to any one of the preceding claims, characterized in that it comprises one or more additional oxidation bases selected from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases other than the oxidation bases of formula (I) and their addition salts. 20   13. Composition according to any one of the preceding claims wherein the amount of each of the additional oxidation bases is between 0.001 to 10% by weight of the total weight of the dye composition. 25   14. Composition according to any one of the preceding claims, in which the alkyl ether carboxylic acid (s) and their salts are chosen from compounds of the following formula (II): ## STR1 ## in which: R 8 represents a linear or branched C8-C22 alkyl or alkylene radical, a (C8-C9) alkylaryl radical such as a (C8-C9) alkylphenyl radical; A represents an oxygen atom or a group -CO-, -NH- or -CO-O-; B is constituted by a random sequence or blocks of -C3H6O- units and -C2H4O- units; N 'is an integer from 1 to 30; p 'is an integer from 0 to 15; Q is an integer equal to 0 or 1; X 'denotes a hydrogen atom or else Na, K, Li, V2 Mg or a monoethanolamine, ammonium or triethanolamine residue.   15. Composition according to the preceding claim, characterized in that, in formula (II), R8 denotes a C8-C22 alkyl radical, preferably C10-C18, A represents an oxygen atom, X 'denotes an atom of hydrogen or sodium, p '= 0, n' ranges from 1 to 20, and preferably 1 to 10, and q 'is 0 or 1.   16. A composition according to any one of the preceding claims wherein the alkyl polyglucoside (s) are represented by the following general formula: wherein R 9 represents an alkyl radical and / or linear or branched alkylene having from about 12 to 30 carbon atoms, an alkylphenyl radical in which the linear or branched alkyl radical contains from 12 to 30 carbon atoms, Rio represents one or more alkylene radicals containing about 2 to 4 carbon atoms, G represents a sugar unit comprising from 5 to 6 carbon atoms, t 'denotes a value ranging from 0 to 10, preferably 0 to 4, and v denotes a value ranging from 1 to 15.   17. Composition according to any one of the preceding claims wherein the monoglycerol or polyglycerolated surfactant (s) are chosen from the compounds of the following formulas: R11O [CH2CH (CH2OH) O] mH; R11O [CH2CH (OH) CH2O] mH or R11O [CH (CH2OH) CH2O] mH; in which R 11 represents a linear or branched, saturated or unsaturated hydrocarbon radical containing from 8 to 40 carbon atoms and preferably from 10 to 30 carbon atoms; m is a number between 1 and 30   18. Composition according to claim 17, characterized in that R11 comprises heteroatoms.   19. A composition according to claim 17 or 18, characterized in that R11 denotes a C10-C20 alkyl or alkylene radical, optionally mono or polyhydroxy.   20. Composition according to any one of the preceding claims, characterized in that the surfactant or surfactants are chosen from lauryl ether carboxylic acid, (C12 / C14 / C16 68/26/6) polyglucoside alkyl, and polyglycerolated cetearyl alcohol having r moles of glycerol, r being an integer of 2 to 10.   21. Composition according to any one of the preceding claims, characterized in that the surfactant (s) are each present in an amount of between 0.01% and 30% by weight relative to the total weight of the dyeing composition.   22. Composition according to any one of the preceding claims, comprising one or more oxidizing agents.   23. Composition according to claim 22, characterized in that the oxidizing agent is chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts, peracids and oxidase enzymes. 15   24. Process for the oxidation dyeing of keratin fibers, characterized in that a dye composition as defined in any one of Claims 1 to 21 is applied to the fibers in the presence of an oxidizing agent for a time sufficient to develop the desired color. 20   25. The method of claim 24, characterized in that the oxidizing agent is selected from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts, peracids and oxidase enzymes.   26. Multi-compartment device in which a first compartment 25 contains a dye composition as defined in any one of claims 1 to 21 and a second compartment contains an oxidizing agent.   27. Use for the oxidation dyeing of keratinous fibers of a composition as defined in any one of claims 1 to 21.